Intramolecularly remote functional group migration reactions involving free radicals.

The application of rearrangement reactions offers opportunities for the efficient construction of complex molecules that are challenging to obtain through conventional synthetic methods. However, the development of radical-mediated rearrangements has lagged far behind that of ionic-type rearrangements, due to the uncontrollability of radical species. Along with the recent renaissance in radical chemistry, radical-mediated functional group migration (FGM) reactions provide a versatile platform for the selective incorporation of functional groups across different molecular distances, enabling the construction of intricate molecular architectures. In the past few years, FGM reactions have showcased plentiful reaction modes, rendering precious control in terms of chemo- and regio-selectivities. This feature article summarizes our achievements in radical-mediated FGM reactions, wherein brief discussion of related works from other laboratories is also included. In this feature article, we aim to provide a comprehensive understanding of the progress in this emerging area.